EP2164881A1 - Use of swellable polymer for sealing - Google Patents

Use of swellable polymer for sealing

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Publication number
EP2164881A1
EP2164881A1 EP08750216A EP08750216A EP2164881A1 EP 2164881 A1 EP2164881 A1 EP 2164881A1 EP 08750216 A EP08750216 A EP 08750216A EP 08750216 A EP08750216 A EP 08750216A EP 2164881 A1 EP2164881 A1 EP 2164881A1
Authority
EP
European Patent Office
Prior art keywords
acrylate
meth
polymer
use according
polyalkylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08750216A
Other languages
German (de)
French (fr)
Other versions
EP2164881B1 (en
Inventor
Bardo Schmitt
Mario Gomez
Martina Ebert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Roehm GmbH
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Evonik Roehm GmbH
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Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2164881A1 publication Critical patent/EP2164881A1/en
Application granted granted Critical
Publication of EP2164881B1 publication Critical patent/EP2164881B1/en
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/104—Water-swellable materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof

Definitions

  • the present invention relates to the use of a swellable polymer for sealing.
  • Japanese Patent Application JP 62-129376 proposes a composition suitable for preventing leaks of sewers without releasing water.
  • the composition contains a (meth) acrylate, in particular a magnesium or sodium salt, polyethylene glycol di (meth) acrylate, in particular a water-soluble polyethylene glycol (meth) acrylate, which may contain 20-30 wt .-% mono (meth) acrylate units, and a polymerization catalyst, in particular a redox initiator.
  • European Patent Application EP 0 376 094 describes a gel-forming injection agent for sealing pipelines or structures or for forming water-impermeable soil layers based on hydroxyalkyl esters of acrylic or methacrylic acid and crosslinking monomers.
  • the agent should contain at least 2% by weight of a tertiary amine derived from acrylic or methacrylic acid, which together with the Peroxodisulfate forms an initiator system.
  • multiply ethylenically unsaturated, free-radically polymerizable monomers are in particular diacrylates and dimethacrylates of polyethylene glycols, which should contain as 1 -10 ethylene oxide radicals, and methylene-bis-acrylatamide or methacrylamide, acrylamidomethyl ethers and Methacrylamidomethylether said polyethylene glycols proposed.
  • Japanese Patent Application JP 02-206657 uses a liquid mixture comprising a monomer, e.g. Acrylamide, polyethylene glycol dimethacrylate or n-methylolpropane, a water-absorbent polymer resin and a water-dispersible rubber latex, e.g. B. SBR, NBR, natural rubber or chloroprene rubber contains.
  • a monomer e.g. Acrylamide, polyethylene glycol dimethacrylate or n-methylolpropane
  • a water-absorbent polymer resin e.g. B. SBR, NBR, natural rubber or chloroprene rubber contains.
  • the liquid mixture is reacted with a reaction catalyst to yield the desired water-proofing material.
  • Japanese Patent Application JP 2003193032 A discloses an aqueous solution-based waterproofing agent containing a water-soluble polyalkylene glycol di (meth) acrylate, an anionic electrolyte monomer, an alcohol having two or more hydroxyl groups, and a polymerization catalyst.
  • the weight ratio of the polyalkylene glycol di (meth) acrylate to the anionic electrolyte monomer should be in the range of 98: 2 to 40:60.
  • the proportion of the anionic electrolyte monomer is 5-70 wt .-%, based on the total weight of the solution.
  • Japanese Patent Application JP 62-022882 A describes a waterproofing agent containing a redox polymerization initiator, a polyethylene glycol di (meth) acrylate having 2 to 50 repeating units, an anionic electrolyte monomer and a cationic electrolyte monomer in certain proportions.
  • European Patent Application EP 0 470 008 A1 relates to a composition based on at least one water-soluble or water-dispersible alkoxyalkyl ester of an unsaturated carboxylic acid.
  • the composition comprises at least one polyalkoxymethoxyethyl methacrylate or acrylate, at least one initiator selected from the group consisting of alkali metal persulfates, ammonium persulfates and hydrogen peroxides, at least one polymerization accelerator and water.
  • the composition can be used in particular for underground sealing.
  • EP 1 616 906 relates to water-swellable sealing compounds of methacrylate monomers, in the examples only (meth) acrylic acid is to be found, which is coextruded.
  • the present invention has the object to show ways to better seal leaks.
  • the sealing materials should in particular be improved Swellability and have the best possible mechanical properties.
  • the sealing should be as simple as possible and can be achieved as quickly as possible.
  • a swellable polymer for sealing obtained by polymerizing a composition containing at least one polyalkylene glycol di (meth) acrylate having a weight average molecular weight greater than 2,500 g / mol, a better predictable manner can be achieved Caulking to achieve leaks.
  • the sealing material is characterized in particular by an improved swellability and the mechanical properties, in particular the tensile strength and the elongation at break, are comparatively good.
  • the sealing can be achieved in a very simple manner and comparatively quickly, and it is possible to achieve an extremely efficient and durable seal.
  • the polymer used according to the invention is both ecologically and health harmless.
  • a swellable polymer is used for sealing.
  • "swellable bar” means that the polymer changes its shape under the action of a solvent and increases its volume
  • preferred solvents are polar compounds with a relative dielectric constant greater than 10, measured at 25 ° C., especially water and water Alcohols having 1 to 4 carbon atoms, with water being particularly preferred becomes.
  • a swelling of at least 150%, in particular of at least 200% can be achieved.
  • the polymer to be used according to the invention is obtainable by polymerization of a composition which comprises at least one polyalkylene glycol di (meth) acrylate having a weight-average molecular weight greater than 2,500 g / mol, preferably in the range from 2,500 to 10,000 g / mol, particularly preferably greater than 5,000 g / mol, especially greater than 8,000 g / mol.
  • the determination of the molecular weight can be carried out in a manner known per se by gel permeation (GPC) or light scattering.
  • GPC gel permeation
  • the determination by means of GPC has proven particularly useful.
  • the polyalkylene glycol di (meth) acrylate preferably comprises ethylene glycol and / or propylene glycol units, the proportion of these units preferably being at least 50.0% by weight, expediently at least 75.0% by weight, in particular at least 90.0% by weight. %, in each case based on the total weight of the polymer.
  • Polyethylene glycol di (meth) acrylate units are particularly preferred.
  • the polymer may optionally have further comonomer units. Preference is given to polymers obtainable by copolymerization with copolymerizable amines and / or hydroxyalkyl esters. Very particularly preferred copolymerizable amines are tertiary amines of the formula (I)
  • R is an alkyl, hydroxyalkyl or alkoxyalkyl radical each having 1 to 4 carbon atoms in the alkyl radical or alkoxy radical, or both R radicals together with the nitrogen atom form a heterocyclic ring and R 'is a hydrogen atom or a methyl group
  • X is an oxygen atom or a group -NR- or -NH-
  • the tertiary amines shown in the formula are preferably water-soluble, substituted esters or amides of acrylic and / or methacrylic acid.
  • n 0
  • n preferably has a value of from 0 to 4, in particular from 0 to 2.
  • radicals R at the tertiary amine nitrogen atom are preferably alkyl or hydroxyalkyl radicals having from 1 to 4 carbon atoms, in particular Both radicals R may together with the nitrogen atom form a preferably 5- or 6-membered heterocycle, for example a pyrrolidine, piperidine or morpholine ring.
  • Particularly preferred tertiary amines are 2-dimethylamino-ethyl-acrylate and - methacrylate, 3- (N, N-dimethylamino) propyl acrylate and methacrylate, 4- (N 1 N-dimethylamino) butyl acrylate and methacrylate, 3 - (N, N-dimethylamino) -propyl-acrylamide and -methacrylamide, triethanolamine-monoacrylate and -monomethacrylate, 2- (dimethylaminoethyloxy) -ethyl-acrylate and -methacrylate, 2-imidazolyl-ethyl-acrylate and -methacrylate, 2-piperazinyl ethyl acrylate and methacrylate, 2-piperazinyl-ethyl-acrylamide and -methacrylamide, N, N-dimethylamino-neopentyl-acrylate and -methacryl
  • Suitable hydroxyalkyl esters of acrylic and / or methacrylic acid are, in particular, water-soluble esters having 2 to 4 carbon atoms in the hydroxyalkyl radical, such as hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, 2- or 4-hydroxybutyl acrylate and methacrylate.
  • the monomers used preferably have a water solubility such that they are an at least 10 wt% total strength at 20 0 C, preferably a 20 wt .-% strength to 60% strength by weight aqueous solution form. Since the dissolved monomers in some cases mutually act as a solubilizer, it is also possible to use or co-use those monomers which are not completely miscible with water alone. However, particularly preferred monomers which are completely miscible at temperatures ranging from -5 ° C to +40 0 C and water are.
  • Polymers which can be used particularly advantageously according to the invention are obtainable by polymerization of a composition which comprises a polyethylene glycol dimethacrylate having a molecular weight M of at least equal to 2,500 g / mol, better still greater than 5,000 g / mol and at least one further (meth) acrylate monomer, in particular (meth) acrylic acid and Amino (meth) acrylates.
  • the use of the polymer to seal a leak can be accomplished in a manner known per se by applying the polymer to the site to be sealed.
  • a procedure is particularly favorable in which a composition comprising at least one polyalkylene glycol di (meth) acrylate having a weight-average molecular weight greater than 1200 g / mol is applied to the leak and polymerized.
  • the polymerization is preferably carried out using a radical-forming initiator at temperatures in the range of 0 0 C to 100 0 C.
  • a radical-forming initiator at temperatures in the range of 0 0 C to 100 0 C.
  • the composition by the addition of 1 wt .-% to 7 wt .-%, based on the total weight of the composition, of a water-soluble inorganic peroxodisulfate, such as alkali or ammonium peroxodisulfate is, at temperatures above 0 0 C, preferably at a temperature cured from 5 ° C to 40 0 C in a short time to form a flexible gel.
  • the curing time is preferably 20 seconds to 120 seconds, but more preferably less than 60 seconds.
  • water-soluble, radical-forming initiators such as tert-butyl hydroperoxide, can be used in an effective amount, provided that they form together with the tertiary amine at low temperatures effective redox system.
  • compositions After admixing the initiator to the site where it is to solidify into a gel.
  • a mixing chamber with a small volume is used, into which the composition and a preferably aqueous solution of the initiator are introduced in such a way that they mix intimately immediately and then arrive immediately at the place of use.
  • the composition should be applied at a concentration at which the radical polymerization directly produces a gel with the desired properties. Suitable is z. B. a concentration of 10 wt .-% to 60 wt .-%, preferably from 20 wt .-% to 40 wt .-% of polymerizable compounds.
  • Plate polymethylates were produced in flat chamber processes in chambers made of glass plates. As distancing 4 mm round cord was used. The polymerization was carried out in a water bath at 60 0 C over a period of 7 hours. After removal of the upper glass plate and the round cord was followed by annealing in a convection oven at 100 0 C for 18 hours.
  • the polymers were stored in distilled water for three days.
  • the test pieces were punched out of the polymer plates in the swollen state.
  • Sample bodies measuring 20x15x4 mm were cut from the plate polymers. These were conditioned in a vacuum oven at 100 ° C for 18 hours. After cooling to room temperature, the samples were weighed body and then stored on stainless steel mesh in clear glass bottles in distilled water (100 ml) in an air-conditioned room at 23 ° C. Periodically, they were removed, adhering liquid was taken up with an absorbent paper, and the polymer pieces were weighed again. The measurement was continued until the maximum swellability was reached. Table 1: Results

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

A method for producing a swellable polymer by polymerizing a composition containing at least one polyalkylene glycol di(meth)acrylate having a weight-average molecular weight from 2500 g/mol to 10000 g/mol, wherein the polymer contains at least 50.0% by weight based on the total weight of the polymer of said at least one polyalkylene glycol di(meth)acrylate.

Description

Verwendung eines quellbaren Polymers zum Abdichten Use of a swellable polymer for sealing
Die vorliegende Erfindung betrifft die Verwendung eines quellbaren Polymers zum Abdichten.The present invention relates to the use of a swellable polymer for sealing.
Stand der TechnikState of the art
Quellbare Polymere und ihre Verwendung in Dichtmassen sind an sich schon bekannt. So schlägt die japanische Patentanmeldung JP 62-129376 eine Zusammensetzung vor, die für die Verhinderung von Undichtigkeiten von Abwasserkanälen ohne Freisetzung von Wasser geeignet ist. Die Zusammensetzung enthält ein (Meth)acrylat, insbesondere ein Magnesium- oder Natriumsalz, Polyethylenglykoldi(meth)acrylat, insbesondere ein wasserlösliches Polyethylenglykol(meth)acrylat, das 20-30 Gew.-% Mono(meth)acrylat-Einheiten enthalten kann, und einen Polymerisationskatalysator, insbesondere einen Redoxinitiator.Swellable polymers and their use in sealants are already known per se. For example, Japanese Patent Application JP 62-129376 proposes a composition suitable for preventing leaks of sewers without releasing water. The composition contains a (meth) acrylate, in particular a magnesium or sodium salt, polyethylene glycol di (meth) acrylate, in particular a water-soluble polyethylene glycol (meth) acrylate, which may contain 20-30 wt .-% mono (meth) acrylate units, and a polymerization catalyst, in particular a redox initiator.
Die europäische Patentanmeldung EP 0 376 094 beschreibt ein gelbildendes Injektionsmittel zum Abdichten von Rohrleitungen oder von Bauwerken oder zur Bildung von wasserundurchlässigen Bodenschichten auf Basis von Hydroxyalkylestern der Acryl- oder Methacrylsäure und vernetzenden Monomeren. Das Mittel soll wenigsten 2 Gew.-% eines von Acryl- oder Methacrylsäure abgeleiteten tertiären Amins enthalten, das zusammen mit dem Peroxodisulfat ein Initiatorsystem bildet. Als vernetzende, mehrfach ethylenisch ungesättigte, radikalisch polymerisierbare Monomere werden insbesondere Diacrylate und Dimethacrylate von Polyethylenglykolen, die möglichst 1 -10 Ethylenoxidreste enthalten sollen, sowie Methylen-bis-acrylatamid oder -methacrylamid, Acrylamidomethylether und Methacrylamidomethylether der genannten Polyethylenglykole vorgeschlagen.European Patent Application EP 0 376 094 describes a gel-forming injection agent for sealing pipelines or structures or for forming water-impermeable soil layers based on hydroxyalkyl esters of acrylic or methacrylic acid and crosslinking monomers. The agent should contain at least 2% by weight of a tertiary amine derived from acrylic or methacrylic acid, which together with the Peroxodisulfate forms an initiator system. As crosslinking, multiply ethylenically unsaturated, free-radically polymerizable monomers are in particular diacrylates and dimethacrylates of polyethylene glycols, which should contain as 1 -10 ethylene oxide radicals, and methylene-bis-acrylatamide or methacrylamide, acrylamidomethyl ethers and Methacrylamidomethylether said polyethylene glycols proposed.
Die japanische Patentanmeldung JP 02-206657 verwendet zum Abdichten von Wasserundichtigkeiten eine flüssige Mischung, die ein Monomer, z. B. Acrylamid, Polyethylenglykoldimethacrylat oder n-Methylolpropan, eines wasserabsorbierenden Polymerharzes und einen wasserdispergierenden Kautschuklatex, z. B. SBR, NBR, Naturkautschuk oder Chloroprenkautschuk, enthält. Die flüssige Mischung wird mit einem Reaktionskatalysator umgesetzt, um das gewünschte Wasserabdichtungsmaterial zu ergeben.Japanese Patent Application JP 02-206657 uses a liquid mixture comprising a monomer, e.g. Acrylamide, polyethylene glycol dimethacrylate or n-methylolpropane, a water-absorbent polymer resin and a water-dispersible rubber latex, e.g. B. SBR, NBR, natural rubber or chloroprene rubber contains. The liquid mixture is reacted with a reaction catalyst to yield the desired water-proofing material.
Die japanische Patentanmeldung JP 2003193032 A offenbart ein Wasserabdichtungsmittel auf Basis einer wässrigen Lösung, die ein wasserlösliches Polyalkylenglykoldi(meth)acrylat, ein anionisches Elektrolytmonomer, einen Alkohol mit zwei oder mehreren Hydroxylgruppen und einen Polymerisationskatalysator enthält. Dabei soll das Gewichtsverhältnis des Polyalkylenglykoldi(meth)acrylates zum anionischen Elektrolytmonomer im Bereich von 98:2 bis 40:60 sein. Der Anteil des anionischen Elektrolytmonomers beträgt 5-70 Gew.-%, bezogen auf das Gesamtgewicht der Lösung.Japanese Patent Application JP 2003193032 A discloses an aqueous solution-based waterproofing agent containing a water-soluble polyalkylene glycol di (meth) acrylate, an anionic electrolyte monomer, an alcohol having two or more hydroxyl groups, and a polymerization catalyst. Here, the weight ratio of the polyalkylene glycol di (meth) acrylate to the anionic electrolyte monomer should be in the range of 98: 2 to 40:60. The proportion of the anionic electrolyte monomer is 5-70 wt .-%, based on the total weight of the solution.
Die japanische Patentanmeldung JP 62-022882 A beschreibt ein wasserabdichtendes Mittel, das einen Redoxpolymerisationsinitiator, ein Polyethylenglykoldi(meth)acrylat mit 2 bis 50 Wiederholungseinheiten, ein anionisches Elektrolytmonomer und ein kationisches Elektrolytmonomer in bestimmten Mengenverhältnissen enthält.Japanese Patent Application JP 62-022882 A describes a waterproofing agent containing a redox polymerization initiator, a polyethylene glycol di (meth) acrylate having 2 to 50 repeating units, an anionic electrolyte monomer and a cationic electrolyte monomer in certain proportions.
Die internationale Patenanmeldung WO 97/03151 betrifft ein Schmiermittel, das ein polymerisierbares, flüssiges Acrylatestermonomer und einen Peroxypolymerisationsinitiator enthält. Bevorzugt werden dabei Polyethylenglykoldimethacrylate als polymerisierbare Polyacrylatester verwendet.International Patent Application WO 97/03151 relates to a lubricant comprising a polymerizable, liquid acrylate ester monomer and a Peroxypolymerisationsinitiator contains. Polyethylene glycol dimethacrylates are preferably used as polymerizable polyacrylate esters.
Die europäische Patenameldung EP 0 470 008 A1 betrifft eine Zusammensetzung auf der Basis mindestens eines wasserlöslichen oder wasserdispergierbaren Alkoxyalkylesters einer ungesättigten Carbonsäure. Die Zusammensetzung umfasst mindestens ein Polyalkoxymethoxyethylmethacrylat oder -acrylat, mindestens einen Initiator aus der Gruppe der Alkalimetallpersulfate, Ammoniumpersulfate und Wasserstoffperoxide, mindestens einen Polymerisationsbeschleuniger und Wasser. Die Zusammensetzung kann insbesondere zum unterirdischen Abdichten verwendet werden.European Patent Application EP 0 470 008 A1 relates to a composition based on at least one water-soluble or water-dispersible alkoxyalkyl ester of an unsaturated carboxylic acid. The composition comprises at least one polyalkoxymethoxyethyl methacrylate or acrylate, at least one initiator selected from the group consisting of alkali metal persulfates, ammonium persulfates and hydrogen peroxides, at least one polymerization accelerator and water. The composition can be used in particular for underground sealing.
Die DE 1974 86 31 beschreibt allgemeine Abdichtungsmassen und erwähnt in einer Tabelle auch die Substanz Polyethylenglycolmethacrylat, das aber eine monofunktionelle Verbindung darstellt. Angaben zum Molekulargewicht der Verbindung fehlen.DE 1974 86 31 describes general sealing compounds and mentions in a table also the substance polyethylene glycol methacrylate, but which is a monofunctional compound. Information on the molecular weight of the compound is missing.
Die DE 422 61 98 beschreibt wasserquellbare Dichtungsmassen aus Methacrylat- Monomeren wie z.B. ethoxyliertes TMPTMA (im Beispiel MG = 1.000, sonst keine weiteren Angaben), die Mischung enthält zusätzlich Polyethylenglykol, das nicht einpolymerisiert wird.DE 422 61 98 describes water-swellable sealing compounds of methacrylate monomers, such as e.g. ethoxylated TMPTMA (in the example MG = 1,000, otherwise no further details), the mixture additionally contains polyethylene glycol, which is not copolymerized.
Die Patentanmeldung EP 1 616 906 betrifft wasserquellbare Dichtmassen aus Methacrylat-Monomeren, in den Beispielen ist nur (Meth)acrylsäure zu finden, die coextrudiert wird.The patent application EP 1 616 906 relates to water-swellable sealing compounds of methacrylate monomers, in the examples only (meth) acrylic acid is to be found, which is coextruded.
Aufgabe und LösungTask and solution
In Anbetracht des Standes der Technik lag der vorliegenden Erfindung die Aufgabe zugrunde, Möglichkeiten zum besseren Abdichten von Undichtigkeiten aufzuzeigen. Dabei sollten die Dichtmaterialien insbesondere eine verbesserte Quellbarkeit sowie möglichst gute mechanische Eigenschaften aufweisen. Weiterhin sollte das Abdichten auf möglichst einfache Art und Weise und möglichst schnell erreicht werden können. Schließlich war es auch ein Ziel der vorliegenden Erfindung, eine möglichst effiziente und dauerhafte Abdichtung zu erreichen.In view of the prior art, the present invention has the object to show ways to better seal leaks. The sealing materials should in particular be improved Swellability and have the best possible mechanical properties. Furthermore, the sealing should be as simple as possible and can be achieved as quickly as possible. Finally, it was also an object of the present invention to achieve a most efficient and durable seal.
Gelöst werden diese sowie weitere nicht explizit genannte Aufgaben, die sich aus den einleitend diskutierten Zusammenhängen zwangsläufig ergeben, durch die Verwendung eines quellbaren Polymers mit allen Merkmalen des vorliegenden Patentanspruchs 1. Besonders zweckmäßige Vorgehensweisen werden in den auf Anspruch 1 rückbezogenen Unteransprüchen beschrieben. Weiterhin wird ein Verfahren zum Abdichten einer Undichtigkeit unter Schutz gestellt.These and other tasks not explicitly mentioned, which inevitably result from the contexts discussed at the outset, are solved by the use of a swellable polymer having all the features of the present patent claim 1. Particularly expedient procedures are described in the subclaims referring back to claim 1. Furthermore, a method for sealing a leak is put under protection.
Dadurch dass man ein quellbares Polymer zum Abdichten verwendet, das durch Polymerisation einer Zusammensetzung erhältlich ist, die mindestens ein Polyalkylenglykol-di(meth)acrylat mit einem gewichtsmittlerem Molekulargewicht größer 2.500 g/mol enthält, gelingt es auf nicht ohne weiteres vorhersehbare Weise, ein besseres Abdichten von Undichtigkeiten zu erreichen. Dabei zeichnet sich das Dichtmaterial insbesondere durch eine verbesserte Quellbarkeit aus und die mechanischen Eigenschaften, insbesondere die Zugfestigkeit und die Bruchdehnung, sind vergleichsweise gut. Weiterhin kann das Abdichten auf äußerst einfache Art und Weise und vergleichsweise schnell erreicht werden und es ist möglich, eine überaus effiziente und dauerhafte Abdichtung zu erreichen. Darüber hinaus ist das erfindungsgemäß eingesetzte Polymer sowohl ökologisch als auch gesundheitlich unbedenklich.By using a swellable polymer for sealing obtained by polymerizing a composition containing at least one polyalkylene glycol di (meth) acrylate having a weight average molecular weight greater than 2,500 g / mol, a better predictable manner can be achieved Caulking to achieve leaks. In this case, the sealing material is characterized in particular by an improved swellability and the mechanical properties, in particular the tensile strength and the elongation at break, are comparatively good. Furthermore, the sealing can be achieved in a very simple manner and comparatively quickly, and it is possible to achieve an extremely efficient and durable seal. In addition, the polymer used according to the invention is both ecologically and health harmless.
Im Rahmen der vorliegenden Erfindung wird ein quellbares Polymers zum Abdichten eingesetzt. „Quellbar" bedeut in diesem Zusammenhang, dass das Polymer unter Einwirkung eines Lösungsmittels seine Gestalt ändert und sein Volumen vergrößert. Für die Zwecke der vorliegenden Erfindung bevorzugte Lösungsmittel sind polare Verbindungen mit einer relativen Dielektrizitätskonstante größer 10, gemessen bei 25°C, insbesondere Wasser und Alkohole mit 1 bis 4 Kohlenstoffatomen, wobei Wasser ganz besonders bevorzugt wird. Zweckmäßigerweise kann eine Quellung von mindestens 150 %, insbesondere von mindestens 200% erreicht werden.In the context of the present invention, a swellable polymer is used for sealing. In this context, "swellable bar" means that the polymer changes its shape under the action of a solvent and increases its volume For the purposes of the present invention, preferred solvents are polar compounds with a relative dielectric constant greater than 10, measured at 25 ° C., especially water and water Alcohols having 1 to 4 carbon atoms, with water being particularly preferred becomes. Conveniently, a swelling of at least 150%, in particular of at least 200% can be achieved.
Das erfindungsgemäß einzusetzende Polymer ist durch Polymerisation einer Zusammensetzung erhältlich, die mindestens ein Polyalkylenglykol-di(meth)acrylat mit einem gewichtsmittleren Molekulargewicht größer 2.500 g/mol, vorzugsweise im Bereich von 2.500 bis 10.000 g/mol, besonders bevorzugt größer 5.000 g/mol, insbesondere größer 8.000 g/mol, enthält.The polymer to be used according to the invention is obtainable by polymerization of a composition which comprises at least one polyalkylene glycol di (meth) acrylate having a weight-average molecular weight greater than 2,500 g / mol, preferably in the range from 2,500 to 10,000 g / mol, particularly preferably greater than 5,000 g / mol, especially greater than 8,000 g / mol.
Die Ermittlung des Molekulargewichts kann dabei auf an sich bekannte Weise durch Gelpermeation (GPC) oder Lichtstreuung erfolgen. Besonders bewährt hat sich die Bestimmung mittels GPC.The determination of the molecular weight can be carried out in a manner known per se by gel permeation (GPC) or light scattering. The determination by means of GPC has proven particularly useful.
Vorzugsweise umfasst das Polyalkylenglykoldi(meth)acrylat Ethylenglykol- und/oder Propylenglykol-Einheiten, wobei der Anteil dieser Einheiten vorzugsweise mindestens 50,0 Gew.-%, zweckmäßigerweise mindestens 75,0 Gew.-%, insbesondere mindestens 90,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Polymers, beträgt. Polyethylenglykoldi(meth)acrylat-Einheiten werden dabei besonders bevorzugt.The polyalkylene glycol di (meth) acrylate preferably comprises ethylene glycol and / or propylene glycol units, the proportion of these units preferably being at least 50.0% by weight, expediently at least 75.0% by weight, in particular at least 90.0% by weight. %, in each case based on the total weight of the polymer. Polyethylene glycol di (meth) acrylate units are particularly preferred.
Das Polymer kann ggf. weitere Comonomer-Einheiten aufweisen. Bevorzugt werden Polymere, die durch Copolymerisation mit copolymehsierbaren Aminen und/oder Hydroxyalkylestern erhältlich sind. Ganz besonders bevorzugte copolymerisierbare Amine sind tertiäre Amine der Formel (I)The polymer may optionally have further comonomer units. Preference is given to polymers obtainable by copolymerization with copolymerizable amines and / or hydroxyalkyl esters. Very particularly preferred copolymerizable amines are tertiary amines of the formula (I)
CH2 = CR' - CO - X - (R" - O)n - R" - NR2 (I)CH 2 = CR '- CO - X - (R "- O) n - R" - NR 2 (I)
worin R einen Alkyl-, Hydroxyalkyl- oder Alkoxyalkylrest, jeweils mit 1 bis 4 Kohlenstoffatomen im Alkylrest oder Alkoxyrest, bedeutet oder beide Reste R zusammen mit dem Stickstoffatom einen heterocyclischen Ring bilden und R' ein Wasserstoffatom oder eine Methylgruppe, X ein Sauerstoffatom oder eine Gruppe -NR- oder -NH- und R" eine Alkylengruppe mit 2 bis 4 Kohlenstoffatomen bedeuten und n eine ganze Zahl von 0 bis 4 ist. Bei den formelnnäßig dargestellten tertiären Aminen handelt es sich vorzugsweise um wasserlösliche, substituierte Ester oder Amide der Acryl- und/oder Methacrylsäure. Im Falle der Acrylsäureabkömmlinge ist R' = H; im Falle der Methacrylsäureabkömmlinge R' = CH3. Die Amide sind wegen ihrer höheren Hydrolysebeständigkeit vor den Estern bevorzugt. Sie enthalten vorzugsweise die Gruppe X = NH. Als Gruppe R" kommen beispielsweise 1 ,2-Propylen-, 1 ,2- und 1 ,4-Butylen- und bevorzugt 1 ,2-Ethylen- und 1 ,3-Propylen-Gruppen in Betracht. In der Regel ist n = 0. Bei esterartigen Verbindungen obiger Formel, also mit X = O, hat n vorzugsweise einen Wert von 0 bis 4, insbesondere von 0 bis 2. Die Reste R am tertiären Amin-Stickstoffatom sind vorzugsweise Alkyl- oder Hydroxyalkylreste mit 1 bis 4 Kohlenstoffatomen, insbesondere Methylgruppen. Beide Reste R können zusammen mit dem Stickstoffatom einen vorzugsweise 5- oder 6- gliedrigen Heterocyclus bilden, z. B. einen Pyrrolidin-, Piperidin- oder Morpholin- Ring.wherein R is an alkyl, hydroxyalkyl or alkoxyalkyl radical each having 1 to 4 carbon atoms in the alkyl radical or alkoxy radical, or both R radicals together with the nitrogen atom form a heterocyclic ring and R 'is a hydrogen atom or a methyl group, X is an oxygen atom or a group -NR- or -NH- and R "denote an alkylene group having 2 to 4 carbon atoms and n is an integer from 0 to 4. The tertiary amines shown in the formula are preferably water-soluble, substituted esters or amides of acrylic and / or methacrylic acid. In the case of acrylic acid derivatives, R '= H; in the case of the methacrylic acid derivatives R '= CH 3 . The amides are preferred over the esters because of their higher hydrolysis resistance. They preferably contain the group X = NH. Suitable groups R "are, for example, 1,2-propylene, 1,2 and 1,4-butylene and preferably 1,2-ethylene and 1,3-propylene groups. In general, n = 0 In the case of ester-type compounds of the above formula, ie with X =O, n preferably has a value of from 0 to 4, in particular from 0 to 2. The radicals R at the tertiary amine nitrogen atom are preferably alkyl or hydroxyalkyl radicals having from 1 to 4 carbon atoms, in particular Both radicals R may together with the nitrogen atom form a preferably 5- or 6-membered heterocycle, for example a pyrrolidine, piperidine or morpholine ring.
Besonders bevorzugte tertiäre Amine sind 2-Dimethylamino-ethyl-acrylat und - methacrylat 3-(N,N-Dimethylamino)-propyl-acrylat und -methacrylat, 4-(N1N- Dimethylamino)-butyl-acrylat und -methacrylat, 3-(N,N-Dimethylamino)-propyl-acrylamid und -methacrylamid, Triethanolamin-monoacrylat und -monomethacrylat, 2-(Dimethylaminoethyloxy)-ethyl-acrylat und -methacrylat, 2-lmidazolyl-ethyl-acrylat und -methacrylat, 2-Piperazinyl-ethyl-acrylat und -methacrylat, 2-Piperazinyl-ethyl-acrylamid und -methacrylamid, N,N-Dimethylamino-neopentyl-acrylat und -methacrylat, N,N-Dimethylamino-neopentyl-acrylamid und -methacrylamid, (1 ,2,2,6,6-Pentamethyl-piperidyl-4)-acrylat und -methacrylat, 3-Morpholino-propyl-acrylamid und -methacrylamid, 2-Morpholino-ethyl-acrylat und -methacrylat, 2-(N,N-Dibutylamino)-ethyl-acrylat und -methacrylat, 4-Diethylamino-1 -methyl-butyl-acrylamid und -methacrylamid. Als Hydroxyalkylester der Acryl- und/oder Methacrylsäure kommen insbesondere wasserlösliche Ester mit 2 bis 4 Kohlenstoffatomen im Hydroxyalkylrest in Betracht, wie Hydroxyethyl-acrylat und -methacrylat, 2-Hydroxypropyl-acrylat und - methacrylat, 2- oder 4-Hydroxybutyl-acrylat und -methacrylat. Auch Hydroxy- (polyalkoxy-alkyl)-ester der Struktur CH2 = CR - CO - O - (Alk - O)x - H, wobei R = H oder CH3, Alk ein Alkylenrest mit 2 bis 4 Kohlenstoffatomen und x eine ganze Zahl von 0 bis 10 ist, sind geeignet.Particularly preferred tertiary amines are 2-dimethylamino-ethyl-acrylate and - methacrylate, 3- (N, N-dimethylamino) propyl acrylate and methacrylate, 4- (N 1 N-dimethylamino) butyl acrylate and methacrylate, 3 - (N, N-dimethylamino) -propyl-acrylamide and -methacrylamide, triethanolamine-monoacrylate and -monomethacrylate, 2- (dimethylaminoethyloxy) -ethyl-acrylate and -methacrylate, 2-imidazolyl-ethyl-acrylate and -methacrylate, 2-piperazinyl ethyl acrylate and methacrylate, 2-piperazinyl-ethyl-acrylamide and -methacrylamide, N, N-dimethylamino-neopentyl-acrylate and -methacrylate, N, N-dimethylamino-neopentyl-acrylamide and -methacrylamide, (1, 2, 2,6,6-Pentamethyl-piperidyl-4) -acrylate and -methacrylate, 3-morpholino-propyl-acrylamide and -methacrylamide, 2-morpholino-ethyl-acrylate and -methacrylate, 2- (N, N-dibutylamino) - ethyl acrylate and methacrylate, 4-diethylamino-1-methyl-butyl-acrylamide and -methacrylamide. Suitable hydroxyalkyl esters of acrylic and / or methacrylic acid are, in particular, water-soluble esters having 2 to 4 carbon atoms in the hydroxyalkyl radical, such as hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, 2- or 4-hydroxybutyl acrylate and methacrylate. Also, hydroxy (polyalkoxy-alkyl) ester of the structure CH 2 = CR - CO - O - (Alk - O) x - H, where R = H or CH 3 , Alk is an alkylene radical having 2 to 4 carbon atoms and x is a whole Number from 0 to 10 is suitable.
Die verwendeten Monomeren weisen vorzugsweise eine derartige Wasserlöslichkeit auf, dass sie insgesamt bei 200C eine wenigstens 10 Gew.- %ige, vorzugsweise eine 20 Gew.-%ige bis 60-Gew-%ige wässrige Lösung bilden. Da die gelösten Monomeren in manchen Fällen wechselseitig als Lösungsvermittler wirken, können auch solche Monomeren verwendet oder mitverwendet werden, die allein mit Wasser nicht vollständig mischbar sind. Besonders bevorzugt sind jedoch Monomere, die bei Temperaturen im Bereich von -5°C bis +400C mit Wasser vollständig mischbar sind.The monomers used preferably have a water solubility such that they are an at least 10 wt% total strength at 20 0 C, preferably a 20 wt .-% strength to 60% strength by weight aqueous solution form. Since the dissolved monomers in some cases mutually act as a solubilizer, it is also possible to use or co-use those monomers which are not completely miscible with water alone. However, particularly preferred monomers which are completely miscible at temperatures ranging from -5 ° C to +40 0 C and water are.
Erfindungsgemäß ganz besonders vorteilhaft einsetzbare Polymere sind durch Polymerisation einer Zusammensetzung erhältlich, die ein Polyethylenglykoldimethacrylat mit einem Molekulargewicht M von mindestens gleich 2.500 g/mol, besser größer 5.000 g/mol und mindestens ein weiteres (Meth)acrylatmonomer enthalten, insbesondere (Meth)acrylsäure und Amino(meth)acrylate .Polymers which can be used particularly advantageously according to the invention are obtainable by polymerization of a composition which comprises a polyethylene glycol dimethacrylate having a molecular weight M of at least equal to 2,500 g / mol, better still greater than 5,000 g / mol and at least one further (meth) acrylate monomer, in particular (meth) acrylic acid and Amino (meth) acrylates.
Die Verwendung des Polymers zum Abdichten einer Undichtigkeit kann im Übrigen auf an sich bekannte Weise erfolgen, indem man das Polymer auf die abzudichtende Stelle aufbringt. Besonders günstig ist jedoch eine Vorgehensweise, bei welcher man eine Zusammensetzung, die mindestens ein Polyalkylenglykol-di(meth)acrylat mit einem gewichtsmittlerem Molekulargewicht größer 1.200 g/mol enthält, auf die Undichtigkeit aufbringt und polymerisiert.Incidentally, the use of the polymer to seal a leak can be accomplished in a manner known per se by applying the polymer to the site to be sealed. However, a procedure is particularly favorable in which a composition comprising at least one polyalkylene glycol di (meth) acrylate having a weight-average molecular weight greater than 1200 g / mol is applied to the leak and polymerized.
Die Polymerisation erfolgt dabei vorzugsweise unter Verwendung eines radikalbildenden Initiators bei Temperaturen im Bereich von 00C bis 1000C. Vorzugsweise wird die Zusammensetzung durch Zusatz von 1 Gew.-% bis 7 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, eines wasserlöslichen anorganischen Peroxodisulfats, wie Alkali- oder Ammonium- peroxodisulfat, bei Temperaturen über 00C, vorzugsweise bei einer Temperatur von 5°C bis 400C in kurzer Zeit unter Bildung eines flexiblen Gels ausgehärtet. Die Härtungszeit beträgt vorzugsweise 20 Sekunden bis 120 Sekunden, besonders bevorzugt jedoch weniger als 60 Sekunden. Neben oder anstelle von Peroxodisulfat können andere wasserlösliche, radikalbildende Initiatoren, wie tert.- Butylhydroperoxid, in einer wirksamen Menge eingesetzt werden, sofern sie zusammen mit dem tertiären Amin ein bei tiefen Temperaturen wirksames Redoxsystem bilden.The polymerization is preferably carried out using a radical-forming initiator at temperatures in the range of 0 0 C to 100 0 C. Preferably, the composition by the addition of 1 wt .-% to 7 wt .-%, based on the total weight of the composition, of a water-soluble inorganic peroxodisulfate, such as alkali or ammonium peroxodisulfate is, at temperatures above 0 0 C, preferably at a temperature cured from 5 ° C to 40 0 C in a short time to form a flexible gel. The curing time is preferably 20 seconds to 120 seconds, but more preferably less than 60 seconds. In addition to or instead of peroxodisulfate, other water-soluble, radical-forming initiators, such as tert-butyl hydroperoxide, can be used in an effective amount, provided that they form together with the tertiary amine at low temperatures effective redox system.
Wegen der sehr schnellen Härtung auch bei tiefer Temperatur sind besondere Vorkehrungen zweckmäßig, um die Zusammensetzung nach dem Zumischen des Initiators an den Einsatzort zu befordern, an dem es sich zu einem Gel verfestigen soll. Man verwendet günstigerweise eine Mischkammer mit geringem Rauminhalt, in die die Zusammensetzung und eine vorzugsweise wässrige Lösung des Initiators so eingeführt werden, dass sie sofort innig vermischen und danach unmittelbar an den Anwendungsort gelangen.Because of the very rapid curing even at low temperature special precautions are appropriate to demand the composition after admixing the initiator to the site where it is to solidify into a gel. Conveniently, a mixing chamber with a small volume is used, into which the composition and a preferably aqueous solution of the initiator are introduced in such a way that they mix intimately immediately and then arrive immediately at the place of use.
Die Zusammensetzung sollte möglichst mit einer Konzentration angewandt werden, bei der durch die radikalische Polymerisation unmittelbar ein Gel mit den gewünschten Eigenschaften entsteht. Geeignet ist z. B. eine Konzentration von 10 Gew.-% bis 60 Gew.-%, vorzugsweise von 20 Gew.-% bis 40 Gew.-% an polymerisierbaren Verbindungen.If possible, the composition should be applied at a concentration at which the radical polymerization directly produces a gel with the desired properties. Suitable is z. B. a concentration of 10 wt .-% to 60 wt .-%, preferably from 20 wt .-% to 40 wt .-% of polymerizable compounds.
Die vorliegende Erfindung wird durch die folgenden Beispiele und Vergleichsbeispiele weiter erläutert, ohne dass hierdurch eine Einschränkung des erfindungsgemäßen Gedanken erfolgen soll.The present invention is further illustrated by the following examples and comparative examples, without thereby limiting the idea of the invention.
Ansatz für die PlattenpolymerisationApproach for plate polymerization
0,20 Gew.-% (0,12 g) 2,2'-Adsobisisobutyronithl (AIBN) 49,9 Gew.-% (29,94 g) Polyethylenglykol-Dimethacrylat0.20% by weight (0.12 g) of 2,2'-adobisisobutyronitrile (AIBN) 49.9 wt .-% (29.94 g) of polyethylene glycol dimethacrylate
29,94 Gew.-% (17,96 g) Acrylsäure29.94% by weight (17.96 g) of acrylic acid
19,96 Gew.-% (11 ,98 g) 2-Dimethylaminoethylmethacrylat19.96% by weight (11.98 g) of 2-dimethylaminoethyl methacrylate
Versuchsbeschreibung PolymerisationExperiment description Polymerization
Es wurden Plattenpolymehsate im Flachkammerverfahren in Kammern aus Glasplatten hergestellt. Als Distanzierung wurde 4 mm Rundschnur verwendet. Die Polymerisation erfolgte im Wasserbad bei 600C über einen Zeitraum von 7 Stunden. Nach Entfernen der oberen Glasplatte und der Rundschnur erfolgte eine Temperung im Umlufttrockenschrank bei 1000C für 18 Stunden.Plate polymethylates were produced in flat chamber processes in chambers made of glass plates. As distancing 4 mm round cord was used. The polymerization was carried out in a water bath at 60 0 C over a period of 7 hours. After removal of the upper glass plate and the round cord was followed by annealing in a convection oven at 100 0 C for 18 hours.
Mechanischen EigenschaftenMechanical properties
Zur Messung der mechanischen Eigenschaften wurden die Polymerisate für drei Tage in destilliertem Wasser gelagert. Die Probekörper wurden in gequollenem Zustand aus den Polymerplatten gestanzt.To measure the mechanical properties, the polymers were stored in distilled water for three days. The test pieces were punched out of the polymer plates in the swollen state.
Versuchsbeschreibung QuellungExperiment description swelling
Aus den Plattenpolymerisaten wurden Probenkörper mit den Maßen 20x15x4 mm zurecht geschnitten. Dieser wurden im Vakuumtrockenschrank bei 100°C für 18 Stunden konditioniert. Nach Abkühlen auf Raumtemperatur wurden die Proben körper gewogen und anschließend auf Edelstahlnetzen in klaren Glasflaschen in destilliertem Wasser (100 ml) im Klimaraum bei 23°C gelagert. In regelmäßigen Abständen wurden sie entnommen, anhaftende Flüssigkeit mit einem saugfähigen Papier aufgenommen und die Polymerstücke erneut gewogen. Die Messung wurde bis zum Erreichen der maximalen Quellbarkeit fortgeführt. Tabelle 1 : ErgebnisseSample bodies measuring 20x15x4 mm were cut from the plate polymers. These were conditioned in a vacuum oven at 100 ° C for 18 hours. After cooling to room temperature, the samples were weighed body and then stored on stainless steel mesh in clear glass bottles in distilled water (100 ml) in an air-conditioned room at 23 ° C. Periodically, they were removed, adhering liquid was taken up with an absorbent paper, and the polymer pieces were weighed again. The measurement was continued until the maximum swellability was reached. Table 1: Results
Die Ergebnisse zeigen, dass die Quellbarkeit der erfindungsgemäßen Beispiele deutlich erhöht ist. Ebenso zeigt die Prüfung zur Bruchdehnung einen deutlich verbesserten Wert. Demgegenüber ist die Zugfestigkeit zwar etwas schlechter jedoch auf vergleichbarem Niveau (ISO527-3/2/25 bei 25 mm Einspannlänge). The results show that the swellability of the inventive examples is significantly increased. Likewise, the test for elongation at break shows a significantly improved value. On the other hand, the tensile strength is somewhat worse, but at a comparable level (ISO527-3 / 2/25 at 25 mm clamping length).

Claims

Patentansprüche: claims:
1. Verwendung eines quellbaren Polymers zum Abdichten, dadurch gekennzeichnet, dass das Polymer durch Polymerisation einer Zusammensetzung erhältlich ist, die mindestens ein Polyalkylenglykol- di(meth)acrylat mit einem gewichtsmittlerem Molekulargewicht größer 2.500 g/mol enthält.1. Use of a swellable polymer for sealing, characterized in that the polymer is obtainable by polymerization of a composition containing at least one polyalkylene glycol di (meth) acrylate having a weight-average molecular weight greater than 2,500 g / mol.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass das Polyalkylenglykoldi(meth)acrylat Ethylenglykol- und/oder Propylenglykol- Einheiten umfasst.2. Use according to claim 1, characterized in that the polyalkylene glycol di (meth) acrylate comprises ethylene glycol and / or propylene glycol units.
3. Verwendung nach Anspruch 2, dadurch gekennzeichnet, dass ein Polyethylenglykoldi(meth)acrylat eingesetzt wird.3. Use according to claim 2, characterized in that a Polyethylenglykoldi (meth) acrylate is used.
4. Verwendung nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Polyalkylenglykol-di(meth)acrylat ein gewichtsmittleres Molekulargewicht größer 5.000 g/mol aufweist.4. Use according to at least one of the preceding claims, characterized in that the polyalkylene glycol di (meth) acrylate has a weight average molecular weight greater than 5,000 g / mol.
5. Verwendung nach mindestens einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Polymer durch Copolymerisation einer Zusammensetzung erhältlich ist, die mit Polyalkylenglykol-di(meth)acrylat copolymerisierbare Amine und/oder Hydroxyalkylester enthält.5. Use according to at least one of the preceding claims, characterized in that the polymer is obtainable by copolymerization of a composition containing polyalkylene glycol di (meth) acrylate copolymerizable amines and / or hydroxyalkyl esters.
6. Verwendung nach Anspruch 5, dadurch gekennzeichnet, dass das Polymer durch Copolymerisation mit mindestens einem tertiären Amin der Formel (I) erhältlich ist6. Use according to claim 5, characterized in that the polymer is obtainable by copolymerization with at least one tertiary amine of the formula (I)
CH2 = CR' - CO - X - (R" - O)n - R" - NR2 (I)CH 2 = CR '- CO - X - (R "- O) n - R" - NR 2 (I)
worin R einen Alkyl-, Hydroxyalkyl- oder Alkoxyalkylrest, jeweils mit 1 bis 4 Kohlenstoffatomen im Alkylrest oder Alkoxyrest, bedeutet oder beide Reste R zusammen mit dem Stickstoffatom einen heterocyclischen Ring bilden und R' ein Wasserstoffatom oder eine Methylgruppe, X ein Sauerstoffatom oder eine Gruppe -NR- oder -NH- und R" eine Alkylengruppe mit 2 bis 4 Kohlenstoffatomen bedeuten und n eine ganze Zahl von 0 bis 4 ist.wherein R is an alkyl, hydroxyalkyl or alkoxyalkyl radical, each having 1 to 4 carbon atoms in the alkyl radical or alkoxy radical, or both radicals R is together with the nitrogen atom form a heterocyclic ring and R 'is a hydrogen atom or a methyl group, X is an oxygen atom or a group -NR- or -NH- and R "is an alkylene group having 2 to 4 carbon atoms and n is an integer from 0 to 4 is.
7. Verwendung nach Anspruch 5 oder 6, dadurch gekennzeichnet, dass das Polymer durch Copolymerisation mit mindestens einem Hydroxyalkylester der Acryl- und/oder der Methacrylsäure erhältlich ist.7. Use according to claim 5 or 6, characterized in that the polymer is obtainable by copolymerization with at least one hydroxyalkyl ester of acrylic and / or methacrylic acid.
8. Verfahren zum Abdichten einer Undichtigkeit, bei welchem man eine Zusammensetzung, die mindestens ein Polyalkylenglykol-di(meth)acrylat mit einem gewichtsmittlerem Molekulargewicht größer 2.500 g/mol enthält, auf die Undichtigkeit aufbringt und polymerisiert.A method for sealing a leak comprising applying and polymerizing a composition containing at least one polyalkylene glycol di (meth) acrylate having a weight average molecular weight greater than 2,500 g / mol to the leakage.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass man die Zusammensetzung unter Verwendung eines radikalbildenden Initiators bei Temperaturen im Bereich von 00C bis 1000C polymerisiert. 9. The method according to claim 8, characterized in that the polymerized using a radical-forming initiator at temperatures in the range of 0 0 C to 100 0 C.
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ES2688532T3 (en) 2013-01-18 2018-11-05 Basf Se Acrylic dispersion based coating compositions
BR112017025558A2 (en) 2015-06-03 2018-08-07 Sika Tech Ag low viscosity vinyl terminated prepolymers with good water solubility
WO2017037227A1 (en) 2015-09-02 2017-03-09 Sika Technology Ag Corrosion-inhibiting, radically cureable composition
JPWO2021107002A1 (en) * 2019-11-29 2021-06-03

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1907666A1 (en) * 1969-02-15 1970-10-15 Merck Patent Gmbh Swellable polymers
JPS57119972A (en) * 1981-01-19 1982-07-26 Asahi Denka Kogyo Kk Water-swelling, water-stopping material
JPS58206680A (en) * 1982-05-26 1983-12-01 Mitsui Toatsu Chem Inc Water-stopping agent
JPS60144235A (en) * 1983-12-29 1985-07-30 Yokohama Rubber Co Ltd:The Tire selecting device
JPS61221281A (en) * 1985-03-27 1986-10-01 Nitto Chem Ind Co Ltd Water stopping agent
JPS61231081A (en) * 1985-04-06 1986-10-15 Mitsui Toatsu Chem Inc Waterproofing agent
JPH0623380B2 (en) 1985-07-24 1994-03-30 日東化学工業株式会社 Waterstop
JPS6234977A (en) * 1985-08-08 1987-02-14 Mitsui Toatsu Chem Inc Water stopping agent
JPS62129376A (en) 1985-12-02 1987-06-11 Toagosei Chem Ind Co Ltd Composition for repairing leakage of water
DE3843440A1 (en) 1988-12-23 1990-06-28 Roehm Gmbh YELLOWING INJECTION AGENT
JPH02206657A (en) 1989-02-03 1990-08-16 Showa Electric Wire & Cable Co Ltd Water stop material
JPH02302488A (en) * 1989-05-18 1990-12-14 Teijin Chem Ltd Anti-fogging composition
FR2665164B1 (en) 1990-07-30 1994-05-06 Rhone Poulenc Chimie AQUEOUS POLYMERIZABLE COMPOSITIONS BASED ON AN ALCOXYALKYL ESTER AND PREPARATION OF SAID ALCOXYALKYL ESTER.
DE4103969A1 (en) * 1991-02-09 1992-08-13 Basf Ag METHOD FOR PRODUCING FINE-PARTICLE, WATER-SOLUBLE OR WATER-SWELLABLE POLYMERISATS
RU2036947C1 (en) * 1991-12-28 1995-06-09 Государственный научно-исследовательский институт химии и технологии полимеров им.акад.В.А.Каргина с опытным заводом Anaerobic hermetic composition
DE4226198A1 (en) * 1992-05-08 1993-11-11 Betonbau Zubehoer Handel Water-swellable sealant material with controllable swelling behaviour - useful for sealing joints or evening out dimensional alternations in the field of structural or civil engineering
WO1997003151A1 (en) 1993-09-27 1997-01-30 Vincent Larry W Compressible graphite lubricant and anaerobic pipe sealant
JPH08283697A (en) * 1995-04-11 1996-10-29 Nippon Shokubai Co Ltd Water cut-off agent for optical cable and composite water cut-off material
JP3621210B2 (en) * 1996-10-09 2005-02-16 三菱レイヨン株式会社 Water-stopping chemical solution and water-stop method using the same
DE19748631A1 (en) 1997-11-04 1999-05-06 Fraunhofer Ges Forschung Safety seal for liquid systems using swellable polymers
JP3970604B2 (en) 2001-12-26 2007-09-05 三菱レイヨン株式会社 Water-stop agent and water-stop method
DE102004032694A1 (en) * 2004-07-06 2006-02-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Swellable material composition and its use
JP4916695B2 (en) * 2005-10-05 2012-04-18 吉佳株式会社 Waterstop composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009007154A1 *

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TWI494420B (en) 2015-08-01
BRPI0814045A2 (en) 2015-02-10
JP5523315B2 (en) 2014-06-18
RU2496795C2 (en) 2013-10-27
DE102007032403A1 (en) 2009-01-22
WO2009007154A1 (en) 2009-01-15
RU2010104102A (en) 2011-08-20
CA2693440C (en) 2015-11-17
CA2693440A1 (en) 2009-01-15
KR101546547B1 (en) 2015-08-21
CN101343527B (en) 2013-04-17
US8309669B2 (en) 2012-11-13
ATE522554T1 (en) 2011-09-15
AU2008274524B2 (en) 2013-09-12
AU2008274524A1 (en) 2009-01-15
JP2010532806A (en) 2010-10-14
TW200918652A (en) 2009-05-01
CN101343527A (en) 2009-01-14
HK1125965A1 (en) 2009-08-21
ES2371301T3 (en) 2011-12-29
KR20100043181A (en) 2010-04-28
US20100163177A1 (en) 2010-07-01

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